title: Macromolecular semi-rigid nanocavities for cooperative recognition of specific large molecular shapes.
abstract: Molecular shape recognition for larger guest molecules (typically over 1 nm) is a difficult task because it requires cooperativity within a wide three-dimensional nanospace coincidentally probing every molecular aspect (size, outline shape, flexibility and specific groups). Although the intelligent functions of proteins have fascinated many researchers, the reproduction by artificial molecules remains a significant challenge. Here we report the construction of large, well-defined cavities in macromolecular hosts. Through the use of semi-rigid dendritic phenylazomethine backbones, even subtle differences in the shapes of large guest molecules (up to ~2 nm) may be discriminated by the cooperative mechanism. A conformationally fixed complex with the best-fitting guest is supported by a three-dimensional model based on a molecular simulation. Interestingly, the simulated cavity structure also predicts catalytic selectivity by a ruthenium porphyrin centre, demonstrating the high shape persistence and wide applicability of the cavity.
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, Yokohama 226-8503, Japan.
authors.forename: Takane
authors.initials: T
authors.lastname: Imaoka
authors.forename: Yuki
authors.initials: Y
authors.lastname: Kawana
authors.forename: Takuto
authors.initials: T
authors.lastname: Kurokawa
authors.forename: Kimihisa
authors.initials: K
authors.lastname: Yamamoto
mesh_terms: D001391:Azo Compounds / Q000737:chemistry*; D003198:Computer Simulation; D056831:Coordination Complexes / Q000737:chemistry*; D050091:Dendrimers / Q000737:chemistry*; D021621:Imaging, Three-Dimensional; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D018716:Molecular Mimicry; D010363:Pattern Recognition, Automated; D011166:Porphyrins / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry; D013816:Thermodynamics; D015032:Zinc / Q000737:chemistry
chemical_list: D001391:Azo Compounds; D056831:Coordination Complexes; D050091:Dendrimers; D011166:Porphyrins; C506824:phenylazomethine; D012428:Ruthenium; D015032:Zinc